Absorption of olefines



April 3, 1934. G. A. KRAMER 3,

ABSORPTION or OLEFINES Filed July 20, 1931 2' Sheets-Sheet 1' lnvenrorfiusTav AKfamer A ril 3, 1934.

G. A. KRAMER ABSORPTION 0F OLEFINES Filed July 20, 1951 2 Sheets-Sheet 2IFIGJ FIG.4

'Flel lnvemor- Gustav A. Kramer UNITED STATES PATENT OFF'IQE ABSORPTIONF OLEFINES Gustav A. Kramer, Oakland, Calif., assignor to ShellDevelopment Company, San Francisco, Calif., acorporation of DelawareApplication July 20, 1931, Serial No. 551,970

15 Claims. (01. 26099.12)

This invention relates to a novel apparatus desired number which whenrevolving, agitate the and process for contacting immiscible liquidsliquid contained in the mixing device, causing inwith each other for thepurpose of extraction, termingling of otherwise not miscible liquids inchemical treatment or the like, and more parmore or less fine emulsions.Diaphragms 25 are ticularly to an apparatus and/or process wherein sospaced that one pair of them form a sub- 60 it is desired to carry outsuch contact in counterstantially enclosed space 26 in which theagicurrent relationship of the two liquids. tation of rotors 24 is notfelt and is of such size The preferred process comprises passing twothat the emulsions formed in the mixing comsubstantially immiscibleliquids in counter-curpartments may separate due to differences in rentflow to each other through a plurality of specific gravity of theliquids in question. 65 stages arranged in contiguous relationship andSuch diaphragms may be also placed between communicating with each ataplurality of points, each end rotor and end plates 11 and 12 of the eachalternate stage containing an agitating mixing vessel, or they may beomitted and exmeans, the end stages being characterized as ternalseparating vessels substituted for this pur- 15 quiescent or separatingzones and each end stage pose. containing an inlet and outlet for theliquids un- The diaphragms 25 are closed on shaft by dergoing treatment.The emulsified liquids in means of diaphragm closing piece 36 whichperthe agitating zones are maintained in a hydromits rotation of theshaft without substantial static balance with the stratified liquidsinthe leakage of fluids between compartments.

20 adjacent separating zones. The agitating and separating stages are in75 The foregoing and other objects and advancommunication throughopenings 27 suitably tages of the invention, however, will be so clearlyplaced near the upper and lower peripheries of apparent to those skilledin the industry, as incithe diaphragms and of such a size that theydental to the following disclosure, that it would permit liquid tocirculate between the two stages serve no useful purpose to furtherenlarge upon without causing the turbulence of the mixing 0 the sameinitially, and with these prefacing re"- zones to be communicated to theseparating marks, therefore, reference will now be had to zones. Vanes34 tend to increase the turbulence the accompanying drawings, generallyillustratand eddy fiow in the agitating compartments ing at least onepractical embodiment of a novel whereas vanes tend to straighten outeddy 30 systematic combination of means for carrying flow in theseparating compartments thereby forth the steps of the method involved,although expediting stratification of the immiscible fluids. notessentially the only apparatus for doing so, Openings 28, 29, 30 and 31are provided for in which drawings feeding into and discharging from thevessel 10, Fig. 1 is a sectional side elevation of the appathe materialsto be inter-acted, while openings 35 ratus carried out according to thisinvention; 32 may be provided for sampling the liquids at Fig. 2 is afront elevation of a diaphragm; various steps of the process. Coil 33may be Fig. 3 is a rear elevation of a diaphragm and provided foradditional internal cooling, either Fig. 4 is a plan view of a diaphragmclosing by water or by other refrigerating media or may piece. beutilized for heating purposes, if so desired,

40 In the drawings, wherein like characters of by the passagetherethrough of hot water, steam reference designate corresponding partsthroughor other heating media. out the several views: 10 is acylindrical shell The operation of the device may possibly be providedwith removable covers 11 and 12 and best understood by first consideringthe rotors at with an outer jacket 13 which may be utilized rest andsupposing that two immiscible liquids 45 for heating or cooling theliquids in the mixer, of different specific gravities, e. g., sulfuricacid should this be necessary. 20 is a shaft running and hydrocarbon oilhave been placed. into the parallel to the center line of shell 10 butpreferapparatus so that practically the entire space ably eccentricallylocated therein and supported. with-in the shell 10 is filled withliquid. The in bearings 21. Stufiing glands 22 preventleaktwo liquidswill naturally rest in the device in 50 age of liquids along the shaftwhen in motion, such a manner that the heavier one occupies a andspecially formed end or ends-of the shaft lower layer, the lighter oneresting on top as, as shown at 23 permit connection to a prime forexample, shown by the dividing line drawn mover by means of pulleys orcouplings or the in Fig. 1. like. The shaft carries within the spaceenclosed If now the rotors are set in motion, the two 55 by vessel 10,suitably spaced rotors 24 of any liquids in the mixing compartments willbe emulsified, but no substantial disturbance of the separated liquidsoccurs in the separating compartments because the total hydraulic headacting on openings 27 from the mixing compartment is still the same asthat from the neighboring separating compartment. If we now remove someof the heavy liquid through opening 31, the deficiency will be made upby additional liquid flowing in through the openings of diaphragm 25.However, this incoming liquid contains not only sulfuric acid, but alsoadmixed hydrocarbon, so that after separation of the two, the level ofsulfuric acid in this compartment will be lower than that correspondingto the hydraulic head necessary to maintain equilibrium. Consequently,some additional liquid will flow into this separating compartmentthrough the lower openings of the diaphragm 25 and some hydrocarbonthrough the upper openings of the diaphragm 25 back into the neighboringmixing compartment, until by separation of the incoming emulsion,sufficient acid has been accumulated to again establish equilibrium.Similarly, if the equilibrium were disturbed by feeding some additionalacid into the opening 29, this acid will again disturb the hydraulicequilibrium and will force more acid through the lower openings of theneighboring diaphragm and so on through the entire device untilequilibrium has again been reached.

By the same way, additional hydrocarbon fed into opening 30 would againbe gradually distributed through the entire system, meanwhile beingsuccessively agitated with acid by the rotors in the mixing chambers.

If hydrocarbon is fed continuously into opening 30 and is beingcontinuously removed at the same rate through opening 28, at the sametime acid is being fed into nozzle 29 and being removed at the same ratethrough nozzle 31, it is easily understood that while the dividinglevels in the separating compartments remain substantially unchanged,the acid and hydrocarbon come into thorough contact with each other incountercurrent, fresh acid always being contacted with nearly fullytreated hydrocarbon and untreated hydrocarbon with nearly fully spentacid.

The relative time of contact may be varied independent of thethroughput. Assume the volu metric capacity of the shell to be 200gallons and that it contains 100 gallons of each liquid, the hourly feedalso being 100 gallons of each. The average contact time of each of theliquids will then be one hour. If the contents of the shell are changedto 50 gallons of the light liquid and 150 gallons of the heavy liquid,the throughput being kept at 100 gallons per hour for each of theliquids, then the average contact time for the light liquid will bereduced to one-half hour and that for .the heavy liquid increased to oneand one-half hours; the ratio of the contact times of the two liquidsthereby.

decreasing from 1 to In similar manner, the relative time of contact ofthe light or heavy liquid may be either increased or decreased,depending on'the character of the substantially immiscible liquids andthe economic conditions of operation.

Under certain circumstances, it may be desirable to effect the contactof the two substantially immiscible fluids by means of parallel flow, inwhich case the lighter fluid is introduced at 30 and removed at the samerate through 28,

while the heavier fluid is fed in at 31 and 18- moved at the same ratethrough 29,

,The number of agitating and settling chambers employed is dependent onthe character of the liquids undergoing treatment and the nature of theprocess. For example, in parallel flow, an agitating chamber incommunication with two settling chambers may suflice whereas incounter-current flow a plurality of agitating chambers is desirable, theefhciency of the process increasing with the number of agitatingcompartments.

By way of example only, reference will be had to the treatment of amineral oil fraction consisting essentially of hydrocarbons containingfour carbon atoms to the molecule with sulfuric acid of such strength,that the tertiary-base olefines contained therein, such as isobutylene,are selectively absorbed by the sulfuric acid and removed therewith,although it is to be understood that the process and apparatus isapplicable to the treatment of any mineral oil fraction containinghydrocarbons of any number of carbon atoms to the molecule with an acidwhich may comprise H2804, H2PO4, HCl, etc.

Pentane-pentene and hexane-hexene fractions are very suitable fortreatment by my process for the selective absorption and removal oftertiary-base olefines (olefines capable of yielding tertiary alcoholsupon hydrolysis).

A butane-butene fraction containing approximately 15 to 20% by wt. oftertiary or gamma butylene is introduced at 30 while an equivalentamount of 65 to H2804 is introduced at 29. To insure the completeabsorption and removal of the gamma butylene, about a 10% excess of 65to 70% H2804 is introduced at 29 (the amount of H2804 to be added beingcalculated on the amount of isobutylene to be absorbed). The vessel 10in the meantime has been filled with 65 to 70% H2804 and thebutane-butene fraction to be treated, the exact proportion of thecontents of the vessel being dependent on the desired relative time ofcontact. The liquids flow in countercurrent fashion, the efilux at 28comprising the butane-butane fraction from which the isobutylene hasbeen substantially removed while the efflux at 31 comprises H2804relatively saturated with isobutylene. The temperature is maintainedbetween about to 90 F. to avoid substantial polymerization of thebutene-l and butane-2. The pressure in the vessel is approximately thevapor pressure of the butane-butene fraction at the operatingtemperature.

The process and/or apparatus assure ease of control, simplicity andflexibility of operation and maximum yield in the optimum minimum timeof contact.

It will be obvious that various substitutions in the materials treatedand in the liquids used, as well as modifications in the order andmanner of execution may be made in the practical application of theinvention, but such substitutions and modifications are to be consideredas comprehended by the above disclosure and included within the purviewof the following claims.

I claim as my invention:

1. A process for the treatment of immiscible fluids comprising: flowinga tertiary-base olefinecontaining fluid and an acid in counter-currentthrough a series of alternate agitating and settling zones only thecontiguous zones of which are in communication with each other, theratioof the hydrostatic heads of the two liquids in the separating zonesbeing at all times substantially equal to the proportions of the twoliquids in the agitating zones and removing the end'product from asettling zone.

2. A process for the treatment or substantially immiscible liquidscomprising: flowing a tertiarybase olefine-containing fluid and an acidin counter-current through a series of alternate agitating and settlingzones each agitating zone being in communication with no more than twosettling zones, the ratio of the hydrostatic heads of the two liquids inthe separating zones being at all times substantially equal to thepropertions of the two liquids in the agitating zones' and removing thedissolved tertiary-base olefine from an end settling zone. I

3. A process for the treatment of substantially immiscible liquidscomprising: flowing a mineral oil fraction containing oleflnes incounter-current with an acid through a series of alternate agitating andsettling zones only the contiguous zones of which are in communicationwith each other, the ratio of the hydrostatic heads of the two liquidsin the separating zones being at all times substantially equal to theproportions oi the two liquids in the agitating zones and removing thetreated material from a settling zone.

4. A process for the treatment of substantially immiscible liquidscomprising: flowing a mineral oil fraction containing oleflnes incounter-current with an acid through a series of alternate agitating andsettling zones each agitating zone being in communication with no morethan two settling zones, the ratio of the hydrostatic heads of the twoliquids in the separating zones being at all times substantially equalto the proportions of the two liquids in the agitating zones andremoving the absorbed tertiary-base oleflnes from an end settling zone.

5. A process for the treatment of substantially immiscible fluidscomprising: flowing a mineral oil fraction consisting essentially ofhydrocarbons containing more than three carbon atoms to the molecule andalso containing the corresponding tertiary-base oleflnes incounter-current with an acid through a series of alternate agitating andsettling zones only the contiguous zones of which are in communicationwith each other, the ratio of the hydrostatic heads of the two liquidsin the separating zones being at all times substantially equal to theproportions of the two liquids in the agitating zones and removing theabsorbed tertiary-base oleflnes from an end settling zone.

6. A process for the treatment'of substantially immiscible liquidscomprising: flowing a mixture of paraflin and olefine hydrocarbonsconsisting essentially of hydrocarbons containing more than three carbonatoms to the molecule and also containing the correspondingtertiary-base oleflnes in counter-current with an acid through a seriesof alternate agitating and settling zones each agitating zone being incommunication with no more than two settling zones, the ratio of thehydrostatic heads of the two liquids in the set tling zones being at alltimes substantially equal to the proportions of the two liquids in theagitating zones and removing the absorbed tertiarybase oleflnes from anend settling zone.

'7. A process for the treatment of substantially immiscible fluidscomprising: flowing a hydrocarbon mixture containing isobutylene incountercurrent with H2SO4 through a series of alternate agitating andsettling zones only the conall times substantially equal to theproportions of the liquids in the agitating zones and removing theabsorbed isobutylene from an end settling zone.

8. A process for the treatment of substantially immiscible fluidscomprising: flowing a hydrocarbon mixture consisting essentially ofCd-Iio and C4H8 and containing isobutylene in countercurrent with H2804through a series of alternate agitating and settling zones eachagitating zone being in communication with no more than two settlingzones, the ratio of the hydrostatic heads 01 the two liquids in theseparating zones being at all times substantially equal to theproportions of the two liquids in the agitating zones andremoving theabsorbed isobutylene from an end settling zone.

9. A process for the treatment of substantially immiscible fluidscomprising: flowing a hydrocarbon mixture conta'ming isobutylene incountercurrent with 65% to H2804 through a series of alternate agitatingand settling zones only the contiguous zones of which are incommunication with each other at a temperature below that at whichpolymerization of secondarybase butylene takes place, the ratio of thehydrostatic heads of the two liquids in the separating zones being, atall times substantially equal to the proportions of the two liquids inthe agitating zones and removing the absorbed isobutylene from an endsettling zone.

10. A process for the treatment 01 substantially immiscible fluidscomprising: flowing a hydrocarbon mixture consisting essentially ofC'lHliJ and 04 H3 and containing isobutylene in countercurrent with 65%to 70% H2304 through a series of alternate agitating and settling zoneseach agitating zone being in communication with no more than twosettling zones at a temperature below that at which polymerization ofsecondarybase butylene takes place, the ratio of the hydrostatic headsof the two liquids in the separating zones being at all timessubstantially equal to the proportions of the two liquids in theagitating zones and removing the absorbed isobutylene from an endsettling zone.

11. A process for the treatment of substantially immiscible fluidscomprising: maintaining at a substantially constant level the height ofan acid layer in a settling zone which also contains anolefine-containing fluid substantially immiscible with said acid,agitating the two liquids in'a mixing zone which is in communicationwith only two contiguous settling zones, the ratio of the hydrostaticheads of the two liquids in the settling zone being at all timessubstantially equal to the proportions of the two liquids in the mixingzone and hydrostatically controlling the flow of fluid from the settlingzone to the mixing zone and vice versa while continuously feeding theimmiscible fluids to the treating zones in countercurrent.

12. A process for the treatment of substantially immiscible fluidscomprising: maintaining at a substantially constant level the heights ofacid layers in a series of horizontally arranged, settling zones whichalso contain olefine-containing fluid substantially immiscible with saidacid, continuously agitating the two liquids in a series of mixing zonesalternately disposed with respect to the settling zones and incommunication with no more than two settling zones, the ratio 01' thehydrostatic heads oi. the two liquids in the settling zones being at alltimes substantially equal to the proportions of the two liquids in themixing zones and hydrostatically controlling the flow.

of fluid from the settling zones to the mixing zones and vice versawhile continuously feeding the immiscible fluids to the treating zonesin countercurrent.

13. A process for the treatment of substantially immiscible fluidscomprising: maintaining at a substantially constant level the heights ofacid layers in a series of horizontally arranged settling zones whichalso contain tertiary-base olefinecontaining fluid substantiallyimmiscible with said acid, continuously agitating-the liquids in aseries of mixingzones alternately disposed with respect to the settlingzones and in communication with no more than two settling zones, theratio of the hydrostatic heads of the two liquids in the settling zonesbeing at all times substantially equal to the proportions of the twoliquids in the mixing zones and hydro statically controlling the flow offluid from the settling zones to the mixing zones and vice versa whilecontinuously feeding the immiscible fluids to the treating zones incounter-current.

14. A process for the treatment of substantially immiscible fluidscomprising: maintaining at a substantially constant level the heights ofH2304 layers in a series of horizontally arranged settling zones whichalso contain tertiary-base olefine-containing fluid substantiallyimmiscible with the HzSOi, continuously agitating the liquids in aseries of mixing zones alternately disposed with respect to the settlingzones and in communication with no more than two settling zones, theratio of the hydrostatic heads of .the two liquids in the settling zonesbeing at all times substantially equal to the proportions of the twoliquids in the mixing zones and hydrostatically controlling the flow offluid from the settling zones to the mixing zones and vice versa whilecontinuously feeding the immiscible fluids to the treating zones incounter-current.

15. A process for the treatment of substantially immiscible fluidscomprising: maintaining at a substantially constant level the heights ofH280; layers in a series of horizontally arranged settling zones whichalso contain isobutylene-containing fluid substantially immiscible vnththe H2804, continuously agitating the liquids in a series of mixingzones alternately disposed with respect to the settling zones and incommunication with no more than two settling zones, the ratio of thehydrostatic heads of the two liquids in the settling zones being at alltime substantially equal to the proportions of the two liquids in themixing zones and hydrostatically controlling the flow of fluid from thesettling zones to the mixing zones and vice versa while continuouslyfeeding the immiscible fluids to the treating zones in countercurrent.

GUSTAV h. KRAMER.

